CN1157260C - Preparation method of solid phosphoric acid catalyst for olefine oligopolymerization or hydrocarbylation - Google Patents
Preparation method of solid phosphoric acid catalyst for olefine oligopolymerization or hydrocarbylation Download PDFInfo
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Abstract
The present invention relates to a preparation method of a solid phosphoric acid catalyst for olefine oligomerization or hydrocarbylation. The preparation method mainly overcomes the defects of the previous solid phosphoric acid catalyst which can not be individually activated by aqueous vapor and can not have high activity and high strength simultaneously. The preparation of the catalyst of the present invention adopts a raw material composition and a mixing ratio which are different from those of the previous catalyst, and introduces at least one of elements of B, Al or In and at least one of elements selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or W. The roasted catalyst precursor is activated by aqueous vapor so as to better solve the problems. The preparation method of the present invention can be used in industrial production.
Description
The present invention relates to a kind of preparation method who is used for the solid phosphoric acid catalyst of olefin oligomerization or hydrocarbonylation.
Solid phosphoric acid catalyst (SPAC) is one of widely used catalyzer in the petrochemical industry, be widely used in the reactions such as the oligomerisation of low-carbon alkene, superimposed, hydrocarbonylation, hydration, especially for olefin oligomerization technology, its technology is comparatively ripe, and has good catalytic activity.The preparation method of solid phosphoric acid catalyst mainly comprises dipping and two kinds of methods of blend in the prior art, and pickling process is because the manufacturing cycle is long, and the catalyst reaction activity that makes is not high, is eliminated gradually; Blending method at first reacts polyphosphoric acid and interpolation component at a certain temperature, and this material and siliceous carrier mix evenly in kneading machine, pass through extrusion, drying, roasting process then, obtain catalyst precursor; This catalyst precursor activates with water vapor and Air mixing gas, obtains the catalyzer finished product.It is even that the catalyzer of this method preparation has mixing of materials, and the characteristics that catalyst activity is high are main directions that those skilled in the art study.Because the main drawback of conventional solid phosphoric acid catalyst is that physical strength is low, manipulate easy to wear and efflorescence in the process, the hydrolysis argillization easily takes place, cause the catalyst bed stressor layer to fall and rise comparatively fast, the catalyst life index is not ideal enough, brings very big difficulty for normal industrial application.Therefore, a kind of to have high catalytic activity, highly selective and high-intensity solid phosphoric acid catalyst and preparation method thereof simultaneously be the target that people pursue for a long time in research.
Disclosed a kind of phosphoric acid/active carbon catalyst of patent CN1049373A and coincidence process, the preparation method of phosphoric acid/active carbon catalyst adopts pickling process, the processed active carbon carrier is immersed in the technical pure phosphoric acid, flooded reflux 2～8 hours in 100～110 ℃, through filtering, drying, activation makes the catalyzer finished product.The evaluating catalyst process is: catalyzer packed in 100～140 milliliters of reactors, and 130～230 ℃ of temperature of reaction, reaction raw materials air speed 2.5～5.0hr
-1, under reaction pressure 2.0～6.0MPa condition, mixed olefins or C
4Alkene contacts with catalyzer and carries out building-up reactions and prepare stop bracket gasoline, and the peak rate of conversion of alkene is 72.44%.Phosphorus acid content is 30～60% (weight) in this activated carbon of phosphoric acid catalyzer, axial crushing strength 170 newton of catalyzer/centimetre
2The disclosed solid phosphoric acid catalyst of the document, though have good catalytic activity, its crush strength is obviously on the low side, catalyst stability is relatively poor.
Chinese patent 97106215.3 (CN1187387A) discloses a kind of preparation method of propene oligomerization solid phosphate catalyst, and this catalyzer is made up of following general formula: AB
aC
b(P
2O
5)
c(H
2O)
dA=Si in the formula; B=Cu, Fe, Ni or their mixture; C=B, Sb, Bi or their mixture; A, b, c, d equal the atomicity of 1 o'clock respective element for the A component.Method for preparing catalyst is earlier Vanadium Pentoxide in FLAKES and phosphoric acid to be made polyphosphoric acid under 120～230 ℃, contains P in the polyphosphoric acid by weight percentage
2O
580～85%, polyphosphoric acid and component B and C make phosphoric acid salt under 120～230 ℃, this material is descended and the A component blends at 140～230 ℃, behind the extruded moulding, 100～250 ℃ of drying treatment 1～10 hour, the mixed gas with air and water vapor activated at last, wherein activates air: water vapor mol ratio 0.5～1.5: 1 before the roasting, activation temperature is 200～300 ℃, and soak time is 3～5 hours.This catalyzer is mainly used in propylene oligomerization and produces nonene and laurylene, and the evaluating catalyst process is a raw material with propylene 47.6% (weight) and propane 52.4% (weight), 200 ℃ of temperature of reaction, and reaction raw materials air speed 2.0hr
-1, carrying out propylene oligomerization under the reaction pressure 4.0MPa condition, the propylene peak rate of conversion is 82.1%.The axial crushing strength of catalyzer reached 730 newton/centimetre
2Compare with solid phosphoric acid catalyst in the past, this activity of such catalysts, crushing strength, anti-argillization performance have had than much progress, do not have high catalytic activity and high-intensity requirement simultaneously but also reach the long-term solid phosphoric acid catalyst of pursuing of people.With regard to industrial production, what people pursued is longer catalyst life, can save production cost, and extends manufacture cycle, and obtains the higher propylene per pass conversion and the yield of product simultaneously, could increase the throughput of device like this, increases economic benefit.Need catalyzer to have higher crushing strength and higher catalytic activity to guarantee simultaneously for this reason.
The objective of the invention is in order to overcome the solid phosphoric acid catalyst that exists in the above-mentioned document should not can not have high reactivity and high crush strength separately simultaneously with the solid phosphoric acid catalyst of steam activation and preparation shortcoming, a kind of preparation method of solid phosphoric acid catalyst is provided, this method is simplified catalyst activation production technique, makes the catalyzer of preparation have the characteristics of crush strength height, active high, purpose selectivity of product height and catalyzer long service life simultaneously.
The present invention is achieved through the following technical solutions: a kind of solid phosphoric acid catalyst that is used for olefin oligomerization or hydrocarbonylation, and it is made up of with molar ratio computing following general formula:
SiA
aB
b(P
2O
5)
c·(H
2O)
d
A is selected from least a in boron, aluminium or the indium in the formula;
B is selected from least a in titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or the tungsten;
The value of a is 0.1～1.5;
The value of b is 0.005～0.2;
The value of c is 1.0～2.0;
The value of d is 0.6～1.1;
A, b, c, d equal the atomicity of 1 o'clock respective element for the Si atom.
In the technique scheme, a value preferable range is 0.25～1.3, and b value preferable range value is 0.01～0.16, and c value preferable range is 1.2～1.8, and d value preferable range is 0.7～1.0; The preferred boron of A component is or/and indium, at least a in the preferred titanium of B component, zirconium, vanadium, niobium, chromium, molybdenum or the tungsten, and component A and B introduce with the form of its corresponding oxide compound, oxyhydroxide or its corresponding soluble salt respectively; Si introduces with the form of diatomite or silica gel.The above-mentioned preparation method who is used for the solid phosphoric acid catalyst of olefin oligomerization or hydrocarbonylation may further comprise the steps successively: with 75～88% (with P
2O
5Meter) polyphosphoric acid of mass percent concentration is made polyphosphoric acid salt with the introduction component under 150～240 ℃, then with contain silicon carrier and mix, obtain viscosity bulk material, behind this material extruded moulding, drying was 0.5～5 hour under 150～250 ℃, in 400～700 ℃ of following roastings 0.5～3 hour; Catalyzer with water steam activation after the roasting, activation temperature are 150～300 ℃, and soak time is 0.5～6 hour.
In the technique scheme, steam activation temperature preferable range is 200～250 ℃, and the soak time preferable range is 2～4 hours.
GB/T3635-83 (chemical fertilizer catalyst, molecular sieve, absorbent particles crush strength measuring method) standard method is adopted in catalyzer crushing strength test of the present invention, testing tool is the electronic intensity measuring device of QCY-602, the catalyzer crushing strength of measuring is the broken power of axial compression resistance that unit surface can be born, unit be newton/centimetre
2
The catalyzer physical and chemical index test result of the inventive method preparation: catalyzer free phosphoric acid 10～18% is (with P
2O
5The mass percent meter), total phosphorus 60～66% is (with P
2O
5The mass percent meter), crush strength 900～1200 newton/centimetre
2, ortho-phosphoric acid silicon in the nuclear magnetic resonance measuring catalyzer: tetra-sodium silicon is 4～8 (in the phosphorus atom numbers).
Catalyst activity evaluation of the present invention is carried out in fixed-bed reactor, and reactor is a stainless steel tubular type reactor, 32 * 1000 millimeters of size Φ, 100 milliliters of interior loading catalysts.Adopt alkene (carbon three or C 4 olefin) as reaction raw materials, alkane (carbon three or butane) is made thinner, raw material olefin concentration 30～90% (quality), and all the other are alkane.80～220 ℃ of temperature of reaction, reaction pressure 2.0～6.0MPa, liquid volume air speed 1～5 hour
-1Under the processing condition, raw material olefin is contacted with solid phosphoric acid catalyst olefin oligomerization takes place.
Analysis in the above-mentioned reaction process and method of calculation, be to feed intake stopping reaction after 12 hours, raw material and tail gas sample are answered in negate, according to alkene, alkane quality percentage composition in GB/T3392-82 (the mensuration vapor-phase chromatography of hydrocarbon impurities in propylene) determination and analysis raw material and the tail gas, calculate olefin conversion thus, purpose selectivity of product and yield.Wherein olefin conversion, purpose selectivity of product and yield are defined as follows:
Use the solid phosphoric acid catalyst of the inventive method preparation, be applicable to C fully
3Or/and C
4Alkene oligomerization is produced C
6～C
16Alkene is specially adapted to oligomerization of propene and produces nonene and laurylene, carbon four superimposed production stop bracket gasoline, and the iso-butylene dimerization is produced isooctene, and isopropyl benzene technology is produced in benzene and propylene hydrocarbonylation, all can obtain gratifying effect.
Ortho-phosphoric acid silicon in the solid phosphoric acid catalyst, tetra-sodium silicon have multiple different crystalline phase respectively, and their crystal phase structure is very big to the intensity effect of catalyzer.Method for preparing catalyst of the present invention is selected from boron, aluminium, indium or their mixture owing to adopted and different in the past raw materials by adding in the P-Si system, improved catalyst activity, and obviously improved catalyzer extrusion, moulding process; Simultaneously by in P-Si-B (Al, In) system, introducing at least a element that is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or the tungsten, under described Preparation of Catalyst condition, formed mixture with certain molecular structure, this mixture is through high-temperature roasting, the intermolecular synergy of each element, adjusted the crystalline phase and the ratio of ortho-phosphoric acid silicon, tetra-sodium silicon, thereby the catalyst precursor that makes preparation has a very high crush strength when keeping high catalytic activity.
Solid phosphoric acid catalyst in the past is because intensity is low, anti-argillization ability, need activate with the gas mixture of water vapor and air or nitrogen, should not use the pure water steam activation separately, adopt the catalyst precursor of the inventive method preparation and reach certain ratio mutually with the tetra-sodium silicon wafer owing to have the ortho-phosphoric acid silicon of ideal structure, the crush strength height, can use the direct activation of pure water steam, need not to feed other gas and dilute, simplified activation producing process, hydrolysis relaxes in this catalyst reaction process simultaneously, the acid content of high strength of acid is more in the active constituent, show the reactive behavior height of catalyzer, the good stability of catalyzer, long service life.Catalyzer for example of the present invention is used for propylene oligomerization and produces nonene and laurylene, and propylene conversion can reach 85%, nonene selectivity 67.8%, laurylene selectivity 20.5%, nonene and laurylene overall selectivity 88.3%; This catalyzer is used for benzene and the isopropyl benzene reaction is produced in the propylene hydrocarbonylation, and propylene conversion can reach 94.2%, and behind the liquid product process separate raw materials benzene that reaction obtains, non-aromatics content is less than 1%.Obtained good effect.
The invention will be further elaborated below by embodiment.
[embodiment 1]
In 2000 milliliters of glass beakers, add 1000 gram concentration and be 82% (with P
2O
5The mass percent meter) polyphosphoric acid is heated to 150 ℃, under agitation, slowly adds a certain amount of titanium dioxide, 145 gram boron oxides and polyphosphoric acid respectively and reacts, and makes the polyphosphate mixture; Simultaneously the 260 dry diatomite of gram (bulk specific gravity is less than 0.3) are placed kneading machine, above-mentioned polyphosphate mixture and diatomite were kneaded in kneading machine 4 minutes, blend is even, it is 4 * 6 millimeters cylindrical particle that the powder ball shape material extrusion of gained becomes diameter, then 170 ℃ dry 1 hour down, be positioned in the muffle furnace, in 300 ℃ of constant temperature calcinings 1 hour, be warming up to 550 ℃ of constant temperature calcinings again 1 hour, and naturally cooled to room temperature.Before catalyzer uses, in the stainless steel tubular type activation tower of 50 * 1000 millimeters of the Φ of packing into, feed water vapor in 200 ℃ of activation 2 hours down.The circle phosphoric acid catalyst that makes consists of:
SiB
0.99Ti
0.04(P
2O
5)
1.4·(H
2O)
0.8
Catalyzer materialization test result: free phosphoric acid 15.8% is (with P
2O
5The mass percent meter), total phosphorus 63.1% is (with P
2O
5The mass percent meter), crush strength 1050 newton/centimetre
2, ortho-phosphoric acid silicon in the nuclear magnetic resonance measuring catalyzer: tetra-sodium silicon is 5.3 (in the phosphorus atom numbers).
According to aforesaid evaluating catalyst process, this catalyzer is used for propylene oligomerization, the evaluation processing condition are: 200 ℃ of temperature of reaction, pressure 4.0MPa, liquid volume air speed 2.0 hours
-1, raw material propylene concentration 47% (quality).The evaluating catalyst result is: propylene conversion 84.0%, nonene selectivity 64.4%, laurylene selectivity 20.3%, nonene and laurylene overall selectivity 84.7%.
[embodiment 2]
According to the preparation method of embodiment 1, with zirconium white replacement titanium dioxide, feed water vapor and activate 2 hours down in 200 ℃, activate 1 hour down in 250 ℃ then.The catalyzer that makes consists of:
SiB
0.99Zr
0.04(P
2O
5)
1.4·(H
2O)
0.9
Catalyzer materialization test result: free phosphoric acid 16.4% is (with P
2O
5The mass percent meter), crush strength 1160 newton/centimetre
2, ortho-phosphoric acid silicon in the nuclear magnetic resonance measuring catalyzer: tetra-sodium silicon is 5.7 (in the phosphorus atom numbers).
According to aforesaid evaluating catalyst method, this catalyzer is used for the mixed c 4 oligomerisation reaction of 1-butylene, 2-butylene and iso-butylene, the evaluating catalyst processing condition are: 170 ℃ of temperature of reaction, pressure 3.5MPa, liquid volume air speed 5.0 hours
-1, in material carbon four hydrocarbon, C 4 olefin concentration 58% (quality).The evaluating catalyst result is: C 4 olefin total conversion rate 86%, and oligomerization product octane value RON 99.3, MON 84.5.
[embodiment 3]
According to the preparation method of embodiment 1, add the polyphosphoric acid of 1150 gram same concentrations, replace titanium dioxide with Niobium Pentxoxide, 193 gram boric acid replace 145 gram boron oxides, and the catalyzer that makes consists of:
SiB
0.75Nb
0.10(P
2O
5)
1.6·(H
2O)
0.8
Catalyzer materialization test result: free phosphoric acid 15.7% (P
2O
5By percentage to the quality), crush strength 980 newton/centimetre
2, ortho-phosphoric acid silicon in the nuclear magnetic resonance measuring catalyzer: tetra-sodium silicon is 5.4 (in the phosphorus atom numbers), dipolymer selectivity 94.1%.
According to aforesaid evaluating catalyst method, this catalyzer is used for the oligomerisation reaction of 2-butylene, the evaluating catalyst processing condition are: 180 ℃ of temperature of reaction, pressure 4.0MPa, liquid volume air speed 2.0 hours
-1, in material carbon four hydrocarbon, 2-butylene concentration 85% (quality).The evaluating catalyst result is: 2-butylene transformation efficiency 82%.
[embodiment 4]
According to the preparation method of embodiment 1, replace titanium dioxide with chromium trioxide, 257 gram boric acid replace 145 gram boron oxides, and the catalyzer that makes consists of:
SiB
1.0Cr
0.14(P
2O
5)
1.4·(H
2O)
0.8
According to aforesaid evaluating catalyst method, this catalyzer is used for the alkylation reaction of benzene and propylene, the evaluating catalyst processing condition are: 180 ℃ of temperature of reaction, pressure 3.5MPa, benzene and propylene mol ratio 3.5, liquid volume air speed 4.0 hours
-1, in material carbon three hydrocarbon, density of propylene 60% (quality).The evaluating catalyst result is: propylene conversion 94.2%, and the liquid product of gained, behind separate raw materials benzene, non-aromatics content is less than 1%.
[embodiment 5]
According to the preparation method of embodiment 1, add same concentrations 1250 gram polyphosphoric acid, with Niobium Pentxoxide instead of part titanium dioxide, the catalyzer that makes consists of:
SiB
0.99Ti
0.04Nb
0.012(P
2O
5)
1.7·(H
2O)
0.8
Catalyzer materialization test result: free phosphoric acid 16.8% is (with P
2O
5The mass percent meter), crush strength 1010 newton/centimetre
2, ortho-phosphoric acid silicon in the nuclear magnetic resonance measuring catalyzer: tetra-sodium silicon is 5.4 (in the phosphorus atom numbers).
According to aforesaid evaluating catalyst process, the evaluation processing condition are: 200 ℃ of temperature of reaction, pressure 4.0MPa, liquid volume air speed 2.0 hours
-1, raw material propylene concentration 47% (quality).The evaluating catalyst result is: propylene conversion 85.0%, nonene selectivity 67.8%, laurylene selectivity 20.5%, nonene and laurylene overall selectivity 88.3%.
[comparative example 1]
According to the preparation method of embodiment 1, do not add any B component, replace 145 gram boron oxides with 175 gram boric acid, activate air with the gas mixture of air and water vapor: the water vapor mol ratio is 1.2: 1,200 ℃ of activation temperatures, soak time 3 hours.The catalyzer that makes consists of:
SiB
0.90(P
2O
5)
1.4·(H
2O)
0.8
Catalyzer materialization test result: crush strength 600 newton/centimetre
2
Use the evaluation method identical with embodiment 1, this catalyzer is used for propylene oligomerization, the evaluating catalyst result is: propylene conversion 77%, nonene selectivity 63%, laurylene selectivity 15%, nonene and laurylene overall selectivity 78%.
Claims (5)
1, a kind of solid phosphoric acid catalyst that is used for olefin oligomerization or hydrocarbonylation, it is made up of with molar ratio computing following general formula:
SiA
aB
b(P
2O
5)
c·(H
2O)
d
A is selected from least a in boron, aluminium or the indium in the formula;
B is selected from least a in titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or the tungsten;
The value of a is 0.1～1.5;
The value of b is 0.005～0.2;
The value of c is 1.0～2.0;
The value of d is 0.6～1.1;
A, b, c, d equal the atomicity of 1 o'clock respective element for the Si atom.
2, according to the described solid phosphoric acid catalyst that is used for olefin oligomerization or hydrocarbonylation of claim 1, it is characterized in that a value is 0.25～1.3, the b value is 0.01～0.16, and the c value is 1.2～1.8, and the d value is 0.7～1.0.
3, according to the described solid phosphoric acid catalyst that is used for olefin oligomerization or hydrocarbonylation of claim 1, it is characterized in that A is a boron or/and indium, B is at least a in titanium, zirconium, vanadium, niobium, chromium, molybdenum or the tungsten.
4, may further comprise the steps successively according to the described preparation method who is used for the solid phosphoric acid catalyst of olefin oligomerization or hydrocarbonylation of claim 1: will be with P
2O
5Mass percent meter concentration is 75～88% polyphosphoric acid and component A and B reaction under 150～240 ℃, then with contain silicon carrier and mix, obtain viscosity bulk material, this material is through extruded moulding, drying was 0.5～5 hour under 150～250 ℃, in 400～700 ℃ of following roastings 0.5～3 hour; It is characterized in that the catalyzer with water steam activation after the roasting, activation temperature is 150～300 ℃, and soak time is 0.5～6 hour.
5, according to the described preparation method who is used for the solid phosphoric acid catalyst of olefin oligomerization or hydrocarbonylation of claim 4, it is characterized in that 200～250 ℃ of steam activation temperature, soak time 2～4 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9403149B2 (en) | 2011-09-21 | 2016-08-02 | Clariant Corpoation | Promoted solid phosphoric acid catalysts and methods of use |
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| JP4366338B2 (en) | 2004-07-16 | 2009-11-18 | 新日本石油株式会社 | Solid phosphoric acid catalyst and olefin dimerization method using the same |
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|---|---|---|---|---|
| US9403149B2 (en) | 2011-09-21 | 2016-08-02 | Clariant Corpoation | Promoted solid phosphoric acid catalysts and methods of use |
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